4,5-Dimethyl-2-(2-methylthio)ethyl)-1,3-oxathiolane

ABSTRACT

Described is the genus of methyl(methylthioethyl)-1,3-dioxolanes and oxathiolanes defined according to the structure: ##STR1## wherein X and Y represent sulphur or oxygen with the proviso that at least one of X and Y is oxygen; wherein m is 0 or 1; and wherein R 1  and R 2  are the same or different and each represent hydrogen or methyl and uses of such methyl(methylthioethyl)-1,3-dioxolanes and oxathiolanes in augmenting or enhancing the aroma or taste of foodstuffs.

BACKGROUND OF THE INVENTION

This invention provides methyl(methylthioethyl)-1,3-dioxolanes andoxathiolanes defined according to the generic structure: ##STR2##wherein X and Y represent sulphur or oxygen with the proviso that atleast one of X and Y is oxygen; wherein m is 0 or 1; and wherein R₁ andR₂ are the same or different and each represent hydrogen or methyl anduses thereof in augmenting or enhancing the aroma or taste offoodstuffs.

Artificial flavoring agents for foodstuffs have received increasingattention in recent years. In many areas, such food flavoring agents arepreferred over natural flavoring agents at least in part because of theuniform flavor that may be so obtained. For example, natural foodflavoring agents such as extracts, essences, concentrates and the likeare often subject to wide variation due to changes in the quality, typeand treatment of the raw materials. Such variation can be reflected inthe end product and results in unreliable flavor characteristics anduncertainty as to consumer acceptance and cost. Additionally, thepresence of the natural product in the ultimate food may be undesirablebecause of increased tendency to spoil. This is particularly troublesomein convenience and snack food usage where such products as dips, soups,chips, prepared dinners, canned foods, sauces, gravies and the like areapt to be stored by the consumer for some time prior to use.

The fundamental problem in preparing artificial flavoring agents is thatof achieving as nearly as possible a true flavor reproduction. Thisgenerally proves to be a difficult task since the mechanism forflavoring development in many foods is not understood. This is notablein products having beef broth-like, meat extract-like, hydrolyzedvegetable protein-like, roasted, pot roast, meaty, bloody, oniony,garlic, buttery and mushroom-like taste and aroma nuances.

Reproduction of beef broth-like, meat extract-like, hydrolyzed vegetableprotein-like, roasted, pot roast-like, meaty, bloody, oniony, garlic,buttery and mushroom aroma and taste nuances has been the subject of along and continuous search by those engaged in the production offoodstuffs. The severe shortage of food, especially protein foods, inmany parts of the world has given rise to the need for utilizingnon-meat sources of proteins and making such proteins as palatable andas meat-like as possible. Hence, materials which will closely simulateor exactly reproduce the flavor and aroma of beef broth, hydrolyzedvegetable protein, yeast, meat, chicken soup, bread, garlic, onion andeven pineapple and tomato are required. Furthermore, meat flavors andvegetable flavors have been enhanced previously by the use of suchmaterials as monosodium glutamate. In many diets sodium is not desired.Furthermore, in many diets, the use of the glutamate ion or glutamicacid is not desired. Therefore a need has arisen for a monosodiumglutamate replacer which does not have any glutamate ion present.

Moreover, there are a great many meat containing or meat based foodspresently distributed in a preserved form. Examples of these arecondensed soups, dry soup mixes, dry meat, freeze dried or lyophilizedmeats, packaged gravies and the like. While these products contain meator meat extracts, the fragrance, taste and other organoleptic factorsare often impaired by the processing operation and it is desirable tosupplement or enhance the flavors of these preserved foods withversatile materials which have beef broth-like, meat extract-like,hydrolyzed vegetable protein-like, roasted, pot roast-like, meaty,bloody, onion, garlic and mushroom aroma and taste nuances.

Food flavors in the alkylthioalkanal area are known in the prior art.Thus, various 4-(methylthio)-butanal itself defined according to thestructure: ##STR3## and the diethyl acetal thereof are known foraugmenting or enhancing the aroma or taste of foodstuffs and otherconsumable materials as is taught in U.S. Pat. No. 3,904,556 issued onSept. 9, 1975 (the specification of which is incorporated by referenceherein). Thus, the compound 4-(methylthio)-butanal diethyl acetal istaught in said U.S. Pat. No. 3,904,556 to provide a mushroom, heatedonion flavor with green sweet tomato, oniony and garlic nuances. The4-(methylthio)-butanal itself is taught by said U.S. Pat. No. 3,904,556to provide a mushroom-like, tomato-like, vegetable-like, cheesey andfruity taste.

Alkanes having 3-methylthio moieties are known in the prior art, forexample, that disclosed in Chem. Abstracts, Volume 96, No. 103327yhaving the structure: ##STR4## This abstract is of Tetrahedron Letters,Vol. 22, number 42, pages 4159-4162, 1981, (Title: "Thiosulfonium Ions.Methylthiolation of 3-methylthio-1-butene and cis- andtrans-1-methylthio-2-butene": Kim and Caserio).

Chem. Abstracts, Vol. 96:20080m which is an abstract of Fischer, LiebigsAnn. Chem., 1981 (10), 1899-1902 discloses the compound having thestructure: ##STR5## wherein n is 2, 3 or 4 but does not disclose itsorganoleptic utilities.

Chem. Abstracts, Vol. 84:164792v, (abstract of GermanOffenlegungsschrift No. 2,530,273) discloses the compound having thestructure: ##STR6## but does not disclose its organoleptic utilities.

U.S. Pat. No. 4,153,442 issued on May 8, 1979; U.S. Pat. No. 4,224,051issued on Sept. 23, 1980; and U.S. Pat. No. 4,101,307 issued on June 18,1978 each discloses plant growth regulating materials compounds definedaccording to the generic structure: ##STR7## in which X and Y which maybe the same or different and represent oxygen, sulphur or a radical N--Bwhere B is hydrogen, a lower alkyl radical containing 1 to 4 carbonatoms, an optionally substituted aryl radical or an optionallysubstituted acyl radical containing from 1 to 4 carbon atoms;

R and R' which may be the same or different and represent a lower alkylradical containing from 1 to 4 carbon atoms or an acyl or amido radicalcontaining from 1 to 4 carbon atoms; in addition they may form with##STR8## a cycle corresponding to the formula ##STR9## in which R₁, R₂,R₃ and R₄ which may be the same or different and represent hydrogen, analkyl radical containing from 1 to 4 carbon atoms and optionallysubstituted by a halogen, the radicals NO₂, hydroxy or alkoxy containingfrom 1 to 4 carbon atoms;

A represents either a single bond or an alkylene chain containing from 1to 4 carbon atoms optionally interrupted by an oxygen atom or a groupN--B' where B' represents hydrogen, an optionally halogenated orhydroxylated alkyl group, an acyl group, the hydrocarbon portion ofthese radicals containing from 1 to 4 carbon atoms, or a cycle having incommon with the preceding cycle 1 to 2 carbon atoms and containing from3 to 6 carbon atoms, from 0 to 2 oxygen atoms and/or a group N--B, or acycle corresponding to the formula ##STR10##

Included in this generic structure is the genus defined according to thestructure: ##STR11## Specific compounds set forth in U.S. Pat. Nos.4,153,442, 4,224,051 and 4,101,307 are those having the structure:##STR12## However, these patents do not specifically disclose thecompound having the structure: ##STR13## These patents also do not setforth the criticality of these compounds insofar as their organolepticutilities are concerned nor do they disclose any organoleptic utilitiesof such compounds.

Nagao, et al, Tetrahedron Letters No. 34, pages 3167-3168 (1979)discloses the genus of compounds defined according to the structure:##STR14## in a synthetic route to yield certain ketones. In this genus Rmay be methyl, ethyl, propyl, butyl, tolyl, tolyl methoxy, allyl orphenyl. This genus is not part of the instant invention. Furthermore,the Nagao, et al paper does not disclose the organoleptic uses of suchcompounds.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is the GLC profile for fraction 3 of the distillation product ofthe reaction product of Example I containing the compound having thestructure: ##STR15## (conditions: 10'×0.125" SE-30 column programmed at100°-220° C. at 8° C. per minute).

FIG. 2 is the NMR spectrum for fraction 3 of the distillation product ofthe reaction product of Example I containing the compound having thestructure: ##STR16## (conditions: Field strength: 100 MHz; Solvent:CFCl₃).

FIG. 3 is the GLC profile for fraction 2 of the distillation product ofthe reaction product of Example II containing the compound having thestructure: ##STR17## (conditions: 10'×0.125" SE-30 column programmed at100°-220° C. at 8° C. per minute).

FIG. 4 is the NMR spectrum for fraction 2 of the distillation product ofthe reaction product of Example II containing the compound having thestructure: ##STR18## (conditions: Field Strength: 100 MHz; Solvent:CFCl₃).

FIG. 5 is the GLC profile for fraction 2 of the distillation product ofthe reaction product of Example III containing the compound having thestructure: ##STR19## (conditions: 10'×0.125" SE-30 column programmed at100°-220° C. at 8° C. per minute).

FIG. 6 is the NMR spectrum for fraction 2 of the distillation product ofthe reaction product of Example III containing the compound having thestructure: ##STR20## (conditions: Field Strength: 100 MHz; Solvent:CFCl₃).

FIG. 7 is the GLC profile for fraction 2 of the distillation product ofthe reaction product of Example IV containing the compound having thestructure: ##STR21## (conditions: 10'×0.125" SE-30 column programmed at100°-220° C. at 8° C. per minute).

FIG. 8 is the NMR spectrum for fraction 2 of the distillation product ofthe reaction product of Example IV containing the compound having thestructure: ##STR22## (conditions: Field Strength: 100 MHz; Solvent:CFCl₃).

FIG. 9 is the GLC profile for the crude reaction product of Example Vcontaining the compound having the structure: ##STR23## (conditions:SE-30 column programmed at 100°-220° C. at 8° C. per minute).

FIG. 10 is the GLC profile for fraction 3 of the distillation product ofthe reaction product of Example V containing the compound having thestructure: ##STR24## (conditions: 10'×0.125" SE-30 column programmed at100°-220° C. at 8° C. per minute).

FIG. 11 is the NMR spectrum for fraction 2 of the distillation productof the reaction product of Example V containing the compound having thestructure: ##STR25## (conditions: Field Strength: 100 MHz; Solvent:CFCl₃).

THE INVENTION

The present invention provides methyl(methylthioethyl)-1,3-dioxolanesand oxathiolanes useful for agumenting or enhancing the aroma or tasteof foodstuffs, said methyl(methylthioethyl)-1,3-dioxolanes andoxathiolanes being defined according to the structure: ##STR26## whereinX and Y represent sulphur or oxygen with the proviso that at least oneof X and Y is oxygen; wherein m is 0 or 1; and wherein R₁ and R₂ are thesame or different and each represent hydrogen or methyl as well asmethods for augmenting or enhancing or modifying the organolepticproperties, e.g. taste and aroma, of said foodstuffs.

The methyl(methylthioethyl)-1,3-dioxolanes and oxathiolanes of ourinvention augment or enhance beef broth-like, meat extract-like,hydrolyzed vegetable protein-like, roasted, pot roast-like, meaty,bloody, oniony, garlic, buttery and mushroom aroma and taste nuancesmaking them useful for augmenting or enhancing flavors for suchfoodstuffs as beef broth, hydrolyzed vegetable protein, yeast, meat,chicken soup, bread, pineapple, tomato, garlic, onion, butter andmushroom flavored foodstuffs.

The methyl(methylthioethyl)-1,3-dioxolanes and oxathiolanes of ourinvention defined according to the structure: ##STR27## wherein X and Yrepresent sulphur or oxygen with the proviso that at least one of X andY is oxygen; wherein m is 0 or 1; and wherein R₁ and R₂ are the same ordifferent and each represent hydrogen or methyl may be produced by meansof reacting an alpha,beta-diol or an alpha,gamma-diol or analpha,beta-hydroxythiol, or an alpha,gamma-hydroxythiol definedaccording to the structure: ##STR28## wherein X and Y each representsulphur or oxygen with at least one of X or Y being oxygen; wherein mrepresents 0 or 1; and wherein R₁ and R₂ are the same or different andeach represents hydrogen or methyl with methional having the structure:##STR29## in the presence of a protonic acid catalyst such asparatoluene sulfonic acid, xylene sulfonic acid, methane sulfonic acid,phosphoric acid and concentrated sulfuric acid. The reaction takes placein the presence of a solvent having a boiling point such that thereaction can proceed in a reasonable period of time, e.g. 1-12 hours atatmospheric pressure or pressures somewhat greater than atmosphericpressure (up to 10 atmospheres). The reaction temperature may vary frombetween about 70° C. up to about 140° C. Reaction temperatures greaterthan 140° C. give rise to unnecessary breakdown of reaction product.Reaction temperatures lower than 70° C. give rise to too long a periodof time of reaction. The solvents utilized must be inert to the reactionproduct as well as inert to the reactants. The solvents utilized mustalso have boiling points of between 70° C. and 140° C. since thereaction is to take place under reflux conditions. The reaction solventmust also be capable of being completely removed from the product ondistillation in view of the fact that the reaction products are used asfood flavors for internal consumption. Accordingly, suitable solventsare, for example, cyclohexane, cyclopentane, cyclooctane,1-methylcyclohexane, 1,2-dimethylcyclohexane,1,2,4-trimethylcyclohexane, 2-ethyltetrahydrofuran,2,5-dimethyltetrahydrofuran and the like.

Examples of the products of our invention and their organolepticproperties are as follows:

                  TABLE I                                                         ______________________________________                                        Structure of Compound                                                                         Organoleptic Properties                                       ______________________________________                                         ##STR30##      A beef broth-like, meat extract-like, hydrolyzed vegetable                     protein-like, roasted and pot roast aroma and taste                          profile with a "monosodium glutamate-like" effect at a                        level of 0.01 ppm causing it to be useful in beef broth,                      hydrolyzed vegetable protein, yeast, meat, chicken soup                       and bread flavored foods.                                      ##STR31##      A meaty, hydrolyzed vegetable protein-like aroma with a                       hydrolyzed vegetable protein- like taste at 0.1 ppm                           causing it to be useful in meat, hydrolyzed vegetable                         protein, pineapple and tomato flavored foodstuffs.             ##STR32##      A bloody, roasted, hydrolyzed vegetable                                       protein-like/meaty  aroma with bloody, roasted, hydrolyzed                     vegetable protein- like and cocoa taste nuances at 0.1                       ppm causing it to be useful in meat, hydrolyzed vegetable                     protein, yeast and bread flavored foodstuffs.                  ##STR33##      An oniony, hydrolyzed vegetable protein-like and garlic                       aroma and taste profile at 0.1 ppm causing it to be                           useful in garlic and onion flavored foodstuffs.                ##STR34##      A buttery, roasted, meaty and mushroom-like aroma with                        buttery, roasted and hydrolyzed vegetable protein-like                        taste profile at 5 ppm causing it to be useful in butter,                     mushroom and hydrolyzed vegetable protein flavored                            foodstuffs.                                                   ______________________________________                                    

At the end of the reaction as stated supra, the reaction product isextracted from the reaction mass or the reaction mass is washed, forexample, with saturated sodium chloride. The reaction product is thendistilled preferably by means of vacuum distillation.

Thus, the methyl(methylthioethyl)-1,3-dioxolanes and oxathiolanesproduced according to our invention can be used to alter, vary, fortify,modify, enhance or otherwise improve the organoleptic properties,including flavor and/or aroma of a wide variety of materials which areingested, consumed or otherwise organoleptically sensed.

The term "alter" in its various forms will be understood herein to meanthe supplying or imparting of a flavor character or note to an otherwisebland, relatively tasteless substance or augmenting an existing flavorcharacteristic where the natural flavor is deficient in some regard orsupplementing the existing flavor or aroma impression to modify theorganoleptic character. The materials which are so altered are generallyreferred to herein as consumable materials.

Such methyl(methylthioethyl)-1,3-dioxolanes and oxathiolanes of ourinvention are accordingly useful in flavoring compositions. Flavoringcompositions are herein taken to mean those which contribute a part ofthe overall flavor impression by supplementing or fortifying a naturalor artificial flavor in a material, as well as those which supplysubstantially all the flavor and/or aroma character to a consumablearticle.

The term "foodstuff" as used herein includes both solid and liquidingestible materials for man or animals, which materials usually do, butneed not, have nutritional value. Thus, foodstuffs includes meats,gravies, soups, convenience foods, malt and other alcoholic ornon-alcoholic beverages, milk and dairy products, nut butters such aspeanut butter and other spreads, seafoods including fish, crustaceans,mollusks and the like, candies, breakfast foods, baked goods,vegetables, cereals, soft drinks, snack foods, dog and cat foods, otherveterinary products, and the like.

When the methyl(methylthioethyl)-1,3-dioxolanes and oxathiolanesaccording to this invention are used in a food flavoring composition,they can be combined with conventional flavoring materials or adjuvants.Such co-ingredients or flavoring adjuvants are well known in the art forsuch use and have been extensively described in the literature. Apartfrom the requirement that any such adjuvant material is ingestiblyacceptable, and thus non-toxic or otherwise non-deleterious,conventional materials can be used and broadly include other flavormaterials, vehicles, stabilizers, thickeners, surface active agents,conditioners and flavor intensifiers.

Examples of preferred co-flavoring adjuvants are:

Methyl thiazole alcohol (4-methyl-5-beta-hydroxyethyl thiazole);

2-Methyl butanethiol;

4-Mercapto-2-butanone;

3-Mercapto-2-pentanone;

1-Mercapto-2-propanone;

Benzaldehyde;

Furfural;

Furfural alcohol;

2-Mercapto propionic acid;

Alkyl pyrazine;

Methyl pyrazine;

2-Ethyl-3-methyl pyrazine;

Tetramethyl pyrazine;

Polysulfides;

Dipropyl disulfide;

Methyl benzyl disulfide;

Alkyl thiophenes;

2-Butyl thiophene;

2,3-Dimethyl thiophene;

5-Methyl furfural;

Acetyl furan;

2,4-Decadienal;

Guiacol;

Phenyl acetaldehyde;

δ-Decalactone;

d-Limonene;

Acetoin;

Amyl acetate;

Maltol;

Ethyl butyrate;

Levulinic acid;

Piperonal;

Ethyl acetate;

n-Octanal;

n-Pentanal;

Hexanal;

Diacetyl;

Monosodium glutamate;

Monopotassium glutamate;

Sulphur-containing amino acids, e.g. cysteine;

Hydrolyzed vegetable protein;

2-Methylfuran-3-thiol;

2-Methyldihydrofuran-3-thiol;

2,5-dimethylfuran-3-thiol;

Hydrolyzed fish protein; and

Tetramethyl pyrazine.

The methyl(methylthioethyl)-1,3-dioxolanes and oxathiolanes or thecompositions incorporating them, as mentioned above, can be combinedwith one or more vehicles or carriers for adding them to the particularproduct. Vehicles can be edible or otherwise suitable materials such asethyl alcohol, propylene glycol, water and the like. Carriers includematerials such as gum arabic, carrageenan, other gums and the like. Themethyl(methylthioethyl)-1,3-dioxolanes and oxathiolanes according tothis invention can be incorporated with the carriers by conventionalmeans such as spray-drying, drum-drying and the like. Such carriers canalso include materials for coacervating themethyl(methylthioethyl)-1,3-dioxolanes and oxathiolanes (and otherflavoring ingredients, as present) to provide encapsulated products.When the carrier is an emulsion, the flavoring composition can alsocontain emulsifiers such as mono- and diglycerides or fatty acids andthe like. With these carriers or vehicles, the desired physical form ofthe composition can be prepared.

The quantity of methyl(methylthioethyl)-1,3-dioxolanes and oxathiolanesutilized should be sufficient to impart the desired flavorcharacteristic to the product, but on the other hand, the use of anexcessive amount of the derivative is not only wasteful anduneconomical, but in some instances too large a quantity may unbalancethe flavor or other organoleptic properties of the product consumed. Thequantity used will vary depending upon the ultimate foodstuff; theamount and type of flavor initially present in the foodstuff; andfurther process or treatment steps to which the foodstuff will besubjected; regional and other preference factors; the type of storage,if any, to which the product will be subject; and the preconsumptiontreatment, such as baking, frying and so on, given to the product by theultimate consumer. Accordingly, the terminology "effective amount" and"sufficient amount" is understood in the context of the presentinvention to be quantitatively adequate to alter the flavor of thefoodstuff.

It is accordingly preferred that the ultimate composition contain fromabout 0.001 parts per million (ppm) to about 250 ppm ofmethyl(methylthioethyl)-1,3-dioxolanes and oxathiolanes or mixturesthereof. More particularly, in food compositions it is desirable to usefrom about 0.001 ppm to 100 ppm for enhancing flavors and in certainpreferred embodiments of the invention, from about 0.001 to 50 ppm ofthe derivatives are included to add positive flavors to the finishedproduct.

The amount of methyl(methylthioethyl)-1,3-dioxolanes and oxathiolanes ormixtures thereof of our invention to be utilized in flavoringcompositions can be varied over a wide range depending upon theparticular quality to be added to the foodstuff. Thus, amounts of one ormore derivatives according to the present invention of from about 0.05ppm up to 80 or 90 percent of the total flavoring composition can beincorporated in such compositions. It is generally found to be desirableto include from about 0.05 ppm up to about 0.1 percent of themethyl(methylthioethyl)-1,3-dioxolanes and oxathiolanes in suchcompositions.

The following examples are given to illustrate embodiments of theinvention as it is preferred to practice it. It will be understood thatthese examples are illustrative and the invention is not to beconsidered as restricted thereto except as indicated in the appendedclaims.

All parts, proportions, percentages and ratios used herein are by weightunless otherwise indicated.

EXAMPLE I PREPARATION OF4,5-DIMETHYL-2-[2-(METHYLTHIO)ETHYL]-1,3-OXATHIOLANE

Reaction: ##STR35##

Into a 100 ml reaction flask equipped with spin bar, reflux condenser,heating mantle, hot plate apparatus (with magnetic stirring apparatus)is placed 5 ml cyclohexane, 0.2 grams paratoluenesulfonic acid and 5.3grams (0.05 moles) of 3-mercapto-2-butanol. Over a period of 30 minutes,5.2 grams (0.05 moles) of 3-methylthiopropionaldehyde are added to thereaction mass. The reaction mass is then heated to reflux and water ofreaction is continuously removed during the refluxing of the reactionmass. The reaction takes place over a period of 7 hours. At the end ofthe 7 hours the reaction mass is transferred to a separatory funnel andthe reaction mass is washed with one 50 ml portion of saturated aqueoussodium chloride solution and then dried over anhydrous sodium sulfate.The product is then filtered and distilled on a Microvigreux columnyielding the following fractions:

    ______________________________________                                                  Vapor        Liquid                                                 Fraction  Temp.        Temp.   Vacuum                                         Number    (°C.) (°C.)                                                                          mm/Hg.                                         ______________________________________                                        1         103          111     2                                              2         105          113     2                                              3         105          114     2                                              4         100          120     2                                              ______________________________________                                    

FIG. 1 is the GLC profile for fraction 3 of the above distillationcontaining the compound having the structure: ##STR36## (conditions:10'×0.125" SE-30 column programmed at 100°-220° C. at 8° C. per minute).

FIG. 2 is the NMR spectrum for fraction 3 of the foregoing distillationcontaining the compound having the structure: ##STR37## (conditions:Field Strength: 100 MHz; Solvent: CFCl₃).

EXAMPLE II PREPARATION OF4,5-DIMETHYL-2-[2-(METHYLTHIO)ETHYL]-1,3-DIOXOLANE

Reaction: ##STR38##

Into a 100 ml reaction flask equipped with spin bar, reflux condenser,heating mantle and hot plate with magnetic stirring apparatus is placed5 ml cyclohexane, 0.2 grams para-toluenesulfonic acid and 3.5 grams(0.04 moles) of 2,3-butanediol. Over a period of 30 minutes, 4.1 grams(0.04 moles) of 3-methylthiopropionaldehyde is added to the reactionmass. The reaction mass is then heated to reflux and refluxed for aperiod of 7 hours during which water of reaction is removed.

The reaction mass is transferred to a separatory funnel and washed withone 50 ml portion of saturated sodium chloride solution and then driedover anhydrous sodium sulfate, filtered and distilled on a Microvigreuxcolumn yielding the following two fractions:

    ______________________________________                                                  Vapor        Liquid                                                 Fraction  Temp.        Temp.   Vacuum                                         Number    (°C.) (°C.)                                                                          mm/Hg                                          ______________________________________                                        1         78           86      2                                              2         76           90      2                                              ______________________________________                                    

FIG. 3 is the GLC profile for fraction 2 of the foregoing distillationcontaining the compound having the structure: ##STR39## (conditions:10'×0.125" SE-30 column programmed at 100°-220° C. at 8° C. per minute).

FIG. 4 is the NMR spectrum for fraction 2 of the foregoing distillationcontaining the compound having the structure: ##STR40## (conditions:Field Strength: 100 MHz; Solvent: CFCl₃).

EXAMPLE III PREPARATION OF4-METHYL-2-[2-(METHYLTHIO)ETHYL]-1,3-DIOXOLANE

Reaction: ##STR41##

Into a 100 ml reaction flask equipped with spin bar, reflux condenser,heating mantle and hot plate with magnetic stirring apparatus is placed5 ml cyclohexane, 0.2 grams para-toluenesulfonic acid and 3.8 grams(0.05 moles) of 1,2-propanediol. Over a period of 8 hours,3-methylthiopropionaldehyde is added to the reaction mass. The reactionmass is then heated to reflux and during refluxing water of formation isremoved. The refluxing continues for a period of 7 hours. At the end ofthe 7 hour period, the reaction mass is transferred to a separatoryfunnel and washed with one 50 ml portion of saturated aqueous sodiumchloride solution and then dried over anhydrous sodium sulfate, filteredand distilled on a Microvigreux column yielding the following fractions:

    ______________________________________                                                  Vapor        Liquid                                                 Fraction  Temp.        Temp.   Vacuum                                         Number    (°C.) (°C.)                                                                          mm/Hg.                                         ______________________________________                                        1         79           85      2                                              2         79           87      2                                              3         75           90      2                                              ______________________________________                                    

FIG. 5 is the GLC profile for fraction 2 of the foregoing distillationcontaining the compound having the structure: ##STR42## (conditions:10'×0.125" SE-30 column programmed at 100°-220° C. at 8° C. per minute).

FIG. 6 is the NMR spectrum for fraction 2 of the foregoing distillationcontaining the compoound having the structure: ##STR43## (conditions:Field Strength: 100 MHz; Solvent: CFCl₃).

EXAMPLE IV PREPARATION OF 2-[2-(METHYLTHIO)ETHYL]-1,3-DIOXOLANE

Reaction: ##STR44##

Into a 100 ml reaction flask equipped with spin bar, reflux condenser,heating mantle and hot plate with magnetic stirring apparatus is placed5 ml cyclohexane, 0.2 grams para-toluenesulfonic acid and 3.1 grams(0.05 moles) of 1,2-ethanediol. Over a period of 30 minutes, 5.2 grams(0.05 moles) of 3-methylthiopropionaldehyde is added to the reactionmass. The reaction mass is then heated to reflux and during reflux,water of formation is removed. The refluxing continues for a period of 9hours. At the end of the 9 hour period, the reaction mass is cooled andtransferred to a separatory funnel and washed with one 50 ml portion ofsaturated sodium chloride solution. The reaction mass is then dried overanhydrous sodium sulfate, filtered and distilled on a Microvigreuxcolumn yielding the following fractions:

    ______________________________________                                                  Vapor        Liquid                                                 Fraction  Temp.        Temp.   Vacuum                                         Number    (°C.) (°C.)                                                                          mm/Hg.                                         ______________________________________                                        1         72           80      2                                              2         65           90      2                                              ______________________________________                                    

FIG. 7 is the GLC profile for fraction 2 of the foregoing distillationcontaining the compound having the structure: ##STR45## (conditions:10'×0.125" SE-30 column programmed at 100°-220° C. at 8° C. per minute).

FIG. 8 is the NMR spectrum for fraction 2 of the foregoing distillationcontaining the compound having the structure: ##STR46## (conditions:Field Strength: 100 MHz; Solvent: CFCl₃).

EXAMPLE V PREPARATION OF 4-METHYL-2-[2-(METHYLTHIO)ETHYL]-m-DIOXANE

Reaction: ##STR47##

Into a 100 ml reaction flask equipped with spin bar, reflux condenser,heating mantle and hot plate with magnetic stirring apparatus is placed0.2 grams para-toluenesulfonic acid, 5 ml cyclohexane and 4.5 grams of1,3-butanediol. Slowly added to the reaction mass over a period of 30minutes is 3-methylthiopropionaldehyde (5.2 grams; 0.05 moles). Thereaction mass is then heated to reflux and refluxed for a period of 9hours. During the refluxing process, water of reaction is removed fromthe reaction mass. At the end of the 9 hour refluxing period, thereaction mass is then cooled and transferred to a separatory funnel andwashed with one 50 ml portion of saturated sodium chloride solution andthen dried over anhydrous sodium sulfate, filtered and distilled on aMicrovigreux column yielding the following fractions:

    ______________________________________                                                  Vapor        Liquid                                                 Fraction  Temp.        Temp.   Vacuum                                         Number    (°C.) (°C.)                                                                          mm/Hg                                          ______________________________________                                        1         85           95      2                                              2         90           96      2                                              3         80           110     2                                              ______________________________________                                    

FIG. 9 is the GLC profile for the crude reaction product prior todistillation containing the compound having the structure: ##STR48##(conditions: SE-30 column programmed at 100°-220° C. at 8° C. perminute).

FIG. 10 is the GLC profile for fraction 3 of the foregoing distillationcontaining the compound having the structure: ##STR49## (conditions:10'×0.125" SE-30 column programmed at 100°-220° C. at 8° C. per minute).

FIG. 11 is the NMR spectrum for fraction 2 of the foregoing distillationcontaining the compound having the structure: ##STR50## (conditions:Field Strength: 100 MHz; Solvent: CFCl₃).

EXAMPLE VI

The compound having the structure: ##STR51## produced according toExample I is added to a 2% solution of Wyler's "Beef Flavored InstantBouillon" (manufactured by Wyler Foods, Division of Borden, Inc.,Chicago, Ill.)

(Ingredients: salt, hydrolyzed vegetable protein, malto dextrin, sugar,beef fat, water, monosodium glutamate, flavorings, corn sugar, beefextract, caramel color, hydrogenated vegetable fat and U.S. certifiedfood color)

at the rate of 0.1 ppm. The resulting flavor can be described as "beefwith onion and garlic aroma and taste nuances". The onion and garlictaste nuances are enhanced by the addition at the rate of 0.3 ppm ofallyl propyl disulfide or allyl propyl trisulfide. The meaty nuances areenhanced by the addition of the compound having the structure: ##STR52##prepared according to Example IV at the rate of 0.04 ppm. When thecompound having the structure: ##STR53## is added thusly, the "savory"nuances are enhanced and a beef broth-like, meat extract-like,hydrolyzed vegetable protein-like, roasted and pot roast-like aroma andtaste of great intensity is imparted to the soup. The compound havingthe structure: ##STR54## is an excellent replacer for monosodiumglutamate. Indeed, the monosodium glutamate in the ingredient groupingmay be completely removed when the compound having the structure:##STR55## is added even at levels as low as 0.01 ppm.

EXAMPLE VII

A meat gravy is prepared containing 0.2 ppm by weight of the compoundhaving the structure: ##STR56## prepared according to Example III, usinga beef base and beef fat. The resulting beef gravy is then added tomushrooms cooked using boiling water at a rate of 10 parts gravy to 100parts cooked mushrooms. The resulting mushroom platter has an excellentnatural-like meaty, hydrolyzed vegetable protein-like, savory mushroomflavor. The flavor is even further enhanced when tomato sauce is addedto the mixture. The flavor is still more enhanced with 2-n-butylthiazoleat the rate of 0.02 ppm is added to the gravy.

EXAMPLE VIII GRAVY FLAVOR

A gravy flavoring material is prepared by admixing the followingingredients:

    ______________________________________                                        Ingredients         Parts by Weight                                           ______________________________________                                        Diacetyl (5% solution in                                                                          0.20                                                      propylene glycol)                                                             Furfural            0.20                                                      2-acetyl-3-ethyl pyrazine                                                                         1.00                                                      2-methyl-3-furfuran thiazole                                                                      0.05                                                      Methional           2.00                                                      2,5-dimethyl-3-furan thio acetate                                                                 0.80                                                      ______________________________________                                    

A bench panel of 5 individuals compared the above formulation with onecontaining the compound having the structure: ##STR57## which is addedat the rate of 5 ppm.

The flavor with the compound having the structure: ##STR58## has aroasted, meaty, mushroom aroma and taste profile with pleasant, butterynuances.

When the flavor which includes the compound having the structure:##STR59## is added at the rate of 0.5% to a standard chicken frankfurtercontaining 50 parts by weight of chicken and 50 parts by weight of pork,the chicken nuances are intensified 50% more than without the compoundhaving the structure: ##STR60## and, in addition, roasted, meaty andmushroom nuances are imparted.

What is claimed is:
 1. 2-[2-(methylthio)ethyl]-1,3-oxathiolane havingthe structure: ##STR61##